Utilization of powdered catalysts



Nov. 4, 1947.

l UTILI ZATION 0F POWDERED CATALYSTS Y.1. A. HATTON ETAL 2,430,015

FiledAug. 21, 1945 2 sheets-sheet invenors John A. Hamon Dondd L. Cleveland Norman E. Peer-q 1 Bq Their' Arrornzq g%&f1l

Patented Nov. 1947 2,430,015 FICE UTILIZATION F POWDEBED CATALYSTS John A. Hatton and"Donal|l L. ClevelandLon Beach, and Norman E. Peery, San Francisco,

Calif., signora to Shell Development Company, San Francisco, Calif., a corporation of Delaware Application August 21, 194s, semi Nc. 611,863

This invention relates tothe use of powdered 1v1 Claims. (Cl. ISG-42) catalysts for ell'ecting various treatments and catl alytic conversions and relates more particularly' vto a method for maintaining an improved catalytic activity in such applications of powdered catalysts wherein the activity of the catalyst is maintained above a chosen minimum by the continuous or intermittent replacement of part of the catalyst by fresh catalyst. The process of the invention is applicable only in processes of the described type and is furthermore restricted to application in such processes where the catalyst is one having a microporousstructure affording an available surface of at least about 50 square meters per gram. A particular aspect of the in' vention relates to an improvement in the socalled uidized catalyst technique, particularly as applied to effecting hydrocarbon conversions such as the catalytic cracking of 'hydrocarbon oils.

It is well known that in the use of solid catalysts the amount of reaction and/or effectiveness of the catalyst depends largely upon the available catalytic surface in the reaction zone." Because of this fact, it has been the practice to prepare solid catalysts in a, form alordingfa large available surface. vThe two common methods for accomplishing this are: (1) to prepare the catalyst in a form having a microporous structure as, fory example, by partial leaching, partial dehydrationof gels, and, (2) to put the catalytic agent on the surface of a carrier or supporting material having a microporous structure as, for example, by impregnating such materials as silica One 'of the primary advantages of the use of the catalyst in a powdered state is that the ca*- alyst in this form is most ladapted for continuous operation. However, during use, the catalyst gradually declines in activity and in order to y l maintain a desired conversion level it is the Dractice to continuously or intermittently replace a portion of the catalyst with fresh catalyst. The

gel, activated alumina, activated carbon, etc., with the catalytic agent.'.-For example, by well-known precipitation methods various metal oxide catalysts are produced'withy available surfaces in the order of 50 to 600 square meters per gram and by applying catalyststo such materials as silica gel tion method described by Emmett and Brunauer J.A. C.`S. 59 1553 (1937).

These catalysts canbe used in the form of pel- -lets of suitable size disposed in a i'lxed or moving catalyst bed. However, in many -cases it is much more desirable to ruse them in the form of a powder and many process techniques for the application of such catalyst powders have been described. The applicationof the catalyst in pow-- dered form is particularly advantageous when the catalyst requires frequent regeneration and it is for this reason that the use of powdered catalyst has reached its highest state of development in the eld of hydrocarbon conversions, such in particular as catalytic cracking.

'catalyst is then a mixture of 'fresh and partially `spent catalyst and the equilibrium activity is a function` of the catalyst replacement rate. In order to provide for the catalyst replacement it is the practice to withdraw a portion of the equilibrium catalyst.

,The object o1' the present invention is to provide a method whereby the equilibrium activity of the catalyst in such operations may be maintained at a higher level with a. given catalyst replacement rate.

This object is accomplished according to the process of the invention by withdrawing for replacement a fraction of the catalyst which is be- 'low the equilibrium activity. The fraction of catalyst below equilibrium activity withdrawn .ac-

cording to the process of the invention is sepa-y rated from a more or less representative portion of the equilibrium catalyst by making use of a r l in the electrical properties of the components of the mixture, and in the present case the composition of the spent catalyst and the active catalyst is the same. While it is not desired to be bound by the correctness of any theory advanced to explain this unexpected behavior there is considerable evidence which indicates that the separation in the case of the equilibrium catalyst is based upon diierences in the available vsurface areas of the more active and less active catalyst particles. It is found that catalysts having a microporous structure lose available surface `upon use and that this loss of available surface is approximately proportional to the decline in activity of the catalyst. Thus, for example, in a typical case, silica-alumina catalysts such as presently sed for catalytic cracking, have available surfaces in the order of 400-1000 square meters per gram when fresh, whereas the available surfaces are usually less than square meters pergram when these catalysts are spent. The catalyst surface adsorbs small amounts'of such materials as H2O, SO2, H2SNHs, amines, etc., from the process gases and the presence of these adsorbed materialsapparently alters the behavior of the particles in the electric field.

Thus, the process of the present invention in its broader aspect comprises continuously or intermittently removing a portion of the equilibrium taining the catalytic activity of the main mass "of catalyst at a desired equilibrium value. In a preferred embodiment of the invention loss kof finely divided catalyst from the system with exit gas or vapor streams is retained as low as possible by adequate and efficientcatalyst recovery means, and the withdrawal of catalyst from the system to provide for fresh catalyst' replacement is eil'ected by separating by means of an electric field a fraction'having a lower activity and an average par` ticle size equal to or somewhat larger than that of the equilibrium catalyst.

The, outline of the process of the invention given in the preceding paragraph will be amplified in the following description of a typical operation of a preferred embodiment of the invention,

vnamely the catalytic cracking of a .hydrocarbon oil with a typical high-surface cracking catalyst. To assist in this description, reference is had to the attached drawings, wherein like or similar parts are designated by like reference numbers and wherein:

Figure I is a ilow diagram of a modified iluid catalyst catalytic cracking plant in which the process of the invention may be conducted.

Figure II is a more or less diagrammatic vertical section of the upper part of the regenerator indicated in Figure I showing an arrangement of inner cyclone separators.

Figure III is a more or less diagrammatic vertical section of the lelectrical separator indicated in Figure I.

The drawings are not drawn to any absolute or relative scale and the dimensions and relative arrangement of `the parts may be varied within reasonably wide ranges while still retaining the basic principles 'of operation contemplated.

Referring to the drawing, Figure I, the oil to be cracked, for instance gas oil, enters via line I and pump 2. This oil is preferably preheated, for example, to a temperature of 40G-800 F., by means of a furnace 3 and then passed via line 4 to reactor 5. Minor amounts of catalyst are introduced into this oil stream from lines 22 and 40 or 4I as will be hereinafter described. Just prior to entering the reactor the oil feed is mixed with hot freshly regenerated catalyst from the regenerator standpipe 8. The amount of catalyst introduced into the oil .in this type of cracking unit is usually between 6 and 30 parts by weight. In reactor 5 the oil contacts a bed o1' fluidized catalyst under 4'catalyst from the system; separatingA said re-j out of thetop of the reactor via line Ib to fractionator II, i Y -A I n fractionator I I the product is separated into the desired fractions. 'I'hus gasoline and gas may be removed oyerhead via line I2, light gas oil or naphtha may be removed via line I3, heavy gas il may be removed via line I4, and 'a heavy oil may be removed from the-bottom via line I5. This heavy oil may be passed through a cooler or waste heatuboiler I6 and a part of it recycled back to the fractionator via pump Il and lines I5, I8, I9

and 20 to quench or desupeiheat the feed. This heavy oil sometimes contains some catalyst particles which escaped separation erably passed through `a thickener 9. Relatively clean oil is withdrawn v ia line 2I and the thickened slurry of catalyst isrwithdrawn via line 22 and recycled as described.

A portion of the catalyst in reactor 5 substantiallyequal to the amount of catalyst introduced with the feed is continuously withdrawn from the bottom through standpipe 23 into line 24. This catalyst is picked up by a stream of regeneration air from blower 25 and carried into regenerator l, Regenerator l, as illustrated, is a conventional down-now fluid catalyst regenerator. The air stream passes up through the uidized bed of catalyst in regenerator 'Iv burning combustible deposits from the catalyst.

A portion of hot regenerated catalyst is continuously withdrawn from the regenerator vViav 'standpipe 8 and introduced into the reactor as described.

In order to avoid overheating in the regeneration it is usually necessary to cool the catalyst and this is done by recycling a portion of the catalyst through cooler 26. Thus, catalyst is withdrawn yvia standpipe 21. This catalyst is picked up by a conditions conducive to the desired conversion of I the particular oil feed. In general, the conditions are about as follows:

Tempera- Liquid Hourly Pressure ture Space Velocity Atm.- F.

stream of air and carriedv through the recycle cooler 2S back up into the regenerator. The air stream is produced by blower 25 and ilows via lines 28, 28 vand 3U.

The hot regeneration gases, after passing up through the catalyst bed, pass through internal cyclone 'separators to remove the bulk of the suspended catalyst particles and then pass out of the regenerator via line 3|. A typical arrangement of internal cyclone separators is illustrated in Figure II. Referring to Figure II, the normal level of the fluidized catalyst in the regenerator 'I is indicated. Below this level the catalyst is present as a relatively dense pseudo liquid phase and above this level a small amount of catalyst is present as dust suspended in the gas stream.. The gas stream enters ports 4T of Buell cyclone separators 48. Most of the suspended catalyst particles are separated and fall into a hopper 49 from where they ilow by gravity down through a dip leg 50 which extends below the normal catalyst level into the iluidized bed of catalyst. The gases largely rfreed of catalyst particles Dass vla ducts 5I into second stage cyclone separators 52. Catalyst particles which are collected pass into hopper 53 and then via dip leg 54 back to the main catalyst-mass'. 'Ihe gases substantially free of catalyst leave theregenerator via line 3|. In many cases these two stages of cyclone separators are sufficient to prevent substantial loss of catalyst with the exit gases. However, in many cases, particularly where a Very expensive and very iinelydivided catalyst isused, itis the practice to vsupplement the cyclone separators by a Cottrelltype precipitator. This is illlustrated in Figure I. Thus, the hot regeneration gas is cooledby passl by ,the vcyclone separators in reactor 5; in this case it is prefquite different from thoseof the catalyst.

ing it through a 'waste heat boiler 33 and then passed through Cottrell precipitator 32. This sas feed to the Cottrell precipitator carries in susl pension a .small amount of catalyst i'lnes which escaped separation by the cyclone separators in the regenerator. The catalyst lines collected by the Cottrell precipitator are withdrawn via standpipe 35 and are carried by the air stream via line 30 back to the regenerator where they mix with the main mass of the catalyst.

In order to remove catalyst to provide for .catalyst replacement, a portion of the regenerated catalyst is withdrawn from the regenerator through conditioner 36 and standpipe 31 to an electrical separator 6. In some cases the conditioner 36 may serve merely to cool the hot regen-v erated catalyst down to a temperature vwhich is more suitable for the electrical separation. However, the efiiciency of the electrical separationl step may usually be appreciably increased by Cottrell precipitator are maintained at a minimum. It will also be noted that the material collected by the Cottrell'precipitator is quite different' from that treated in the electrical separator 6. Thus, the material collected by theCottrell precipitator consists of very fine .catalyst particles, whereas the material treated in the electrical separator 6 is a. representative portion of themain catalyst ymass which, if anything, has a slightly higher average particle size than the total catalyst because of theseparation of its further conditioning the catalyst by careful con.- 3

trol of the water content of the gas phase and especially by treating the catalyst with separate agents. Thus, a controlled amount of steam and air may be advantageously introduced into the standpipe 31 via line 36. Also, anelectrolytic agent such as ammonia, vapors of amine or hydrogen fluoride may be introduced in controlled amounts via line 39. Such conditioning agents are adsorbed on the catalyst in proportion to the available catalyst surface and greatly increase the effect of the electrical field upon of one type of electrical separator is illustrated in Figure III. Referring to Figure III, 66 designates the feed hopper provided with a vibrating mechanical feeding screen 6I. By means of this feeding mechanism the catalyst particles are fed in a more or less uniform layer onto the rotating electrically charged roll 62; 63 is a gas-tube electrode; 64 is a brush charging electrode; 65 is an insulating screen; 66 is the adjustable dividing plate; 61 is a brushfor cleaning the roll; and 68 is a vent.

l In separator 6 the catalyst particles are separated into two fractions according to their cata.- lytic activity. The less active fraction is withdrawn via line 40 or 4|. The more active fraction is fed via line 42 or 43 into line l and back 'Ato the reaction system as described. The alternative-lines for withdrawaly of less active and more activevfractions of the catalyst from the separator are provided to allow for differences in the electrical properties ofthe catalysts and to allow for reversal ofthe polarities of the electrodes. t

An amount of fresh catalyst approximately equivalent to the amount of spent catalyst withdrawn from the separator 6 is withdrawn into the system from catalyst storage vessel 44. This catalyst, which may be introduced intermittently or continuously, is withdrawn via standpipe. yl5 and introduced into the system via. line `I6 by the regeneration air.

It will be noted that in the ysystem described there'is no substantial removal of catalyst except y at least apart'of the catalyst fines.

The process of the invention is of general application to all catalyst systems wherein a finely divided catalyst having a large surface area is used and the effectiveness of the catalyst is maintained above a desired equilibrium level by the continuous or intermlttentreplacement of a minor portion of the main catalyst mass by fresh catalyst. Thus, the invention is applicable to liquid phase operation, vapor phase operation and mixed phase operation in both regenerative and non-regenerative processes. Preferred applications of the process are, however, in vapor phase operation with continuous or frequent regeneration of the catalyst since it is in such operations that the loss of available surface of various catalysts is more nearly proportional to the loss of catalytic activity.

As pointed out above, the process of the invention is restricted to application in such operations wherein the fresh catalyst is one having a large available surface. In general, the process is more efficient lthe higher the surface of the fresh catalyst. Examples of catalysts which are particularly suitable are the natural clay catalysts` including those which have been made more active or selective by treatment or modification andthe synthetic clay-type catalysts.l A particular example of the former is the catalyst sold under the trade-name of Filtrol. catalysts are synthetic high-surface materials consisting largely of silica and/or alumina and/ or zirconia and/or magnesia often containing minor amounts of various promoter substances such as boric oxide, aluminum fluoride, aluminum phosdivided, l. e., passing at least a 6-mesh sieve, and should preferably consist largely of particles retained by a 20G-mesh sieve.-v In such cases where a large part of the catalyst consists of particles passing a 20o-mesh sieve, it is possible and advantageous to separate and treat in the electrical separation step only the larger particles. ,-The catalyst particles do not need to be of uniform size: However, a relatively small range of particle. size allows a more' yefficient separation to be made. Thus, in some cases it may be desirable to separate a fraction of a narrow size range by elutriation or sieving and then l treat only this fraction in the electrical separation step.

Particularly suitable catalysts for u se in the present process are the so-called MS catalysts. These catalysts are prepared as small substan- The latter tially uniform spheres otalmost any desired size.- l

Suitable methods for the preparation of such catalysts are described in copending application, Serial No. 492,189,`led June 23, 1943. These catalysts may b'e employed in the-process ofthe present ,invention in carrying out a wide variety of processes and treatments including conversions of inorganic materials aswell as organic materials. A

We claim as our invention: f

l. In the application of a finely divided adsorptive solid catalyst which declines in activity and adsorptive ability in use, the method of maintaining a high activity in substantially continuous operation which comprises substantially continuously withdrawing a, representative portion of the Y catalyst from the main `mass of catalyst, separating said portion by an electrostatic separation treatment into two fractions having different specific surfaces, discarding the fraction having the lower specific surface, returning to the main v catalyst mass the fraction having the higher electric iield, discarding the fraction having the lower specific surface, returning to the main catalyst mass the fraction having the higher speciic surface,'and adding to the main catalyst mass a portion of fresh catalyst substantially equivalent to said discarded fraction.

3. Process according to claim 2 in which the representative portion of thev catalyst separated into two fractions by means of a high potential electric field is conditioned to improve the eiliciency in said separation by treatment with a volatile water-soluble electrolyte which is adsorbed by the catalyst particles.

4. Process vaccording to claim 2 in which the representative portion of the catalyst separated into two fractions by means of a high potential electric field is conditioned to improve the emciency in said separation, by treatment with vapors of an amine. A l

5. Process according to claim 2 in which the representative portion of the catalyst separated into two fractions by means of a high potential electric field is conditioned to improve the efficiency in said separation by treatment with vapors of ammonia.

`6. Process according to claim 2 in which the representative portion ofthe catalyst separated into two fractions by means of a high potential electric eld is conditioned to improve the edil' ciency in said separation by treatment with vapors of hydrogen fiuoride.

7. In the application of a finely divided adsorptive solid catalyst which declines in activity and adsorptive ability in use, the method of Vmainl taining a high activity in substantially continuous operation which comprises substantially continuouslywithdrawing a representative portion of the 'I 8 catalyst from the main mass of catalyst, separating said withdrawn portion into two fractions in` the presence of water vapor by means of a high potential electric field, discarding the fraction having the lower conductivity,` returning the fraction having the higher conductivity to the main catalyst mass, and adding to the main catalyst mass a portion of fresh catalyst substantially equivalent to said discarded fraction.

8. In the application of a nely divided adsorptive solid cracking catalyst in the catalytic cracking of a hydrocarbon oil, the method of maintaining a high activity in substantially continuous operation which comprises substantially continuously withdrawing a representative portion of thecatalyst from the main mass of catalyst, separating said portion by an electrostatic separation treatment into two fractions having different speciic surfaces, discarding the fraction having the lower specific surface, returning to the main catalyst mass the fraction having the higher specic surface, and adding to the main catalyst mass a portion of fresh catalyst substantially equivalent to said discarded fraction.

9. In the application of a nely divided adsorptive siliceous catalyst which declines in activity and adsorptive ability in use, the method of maintaining a high activity in substantially continuous operation which comprises substantially continuously withdrawing a representative portion of the catalyst from the main mass of catalyst, separating said portion by an electrostatic separation treatment into two fractions having different specific surfaces, discarding the fraction having l the lower specific surface, returning to the main catalyst mass the 'fraction having the higher specific surface, and adding to the main catalyst mass a portion of fresh catalyst substantially equivalent to said discarded fraction.

10. In the applicationof a finely divided adsorptive siliceous cracking catalyst in the catalytic cracking 4of a hydrocarbon oil, the method of maintaining a high activity in substantially continuous operation which comprises substantially continuously withdrawing a representative portion of the catalyst from the main mass of catalyst, separating said portion by an electrostatic separation treatment into two fractions having different specific surfaces, discarding the fraction l havingthe lower specic surface, returning to the main catalyst mass the fraction having the higher specific surface, and adding to the main catalyst mass a portion of fresh catalyst substantially equivalent to said discarded fraction.

1l. Process according to claim 10 in which the representative portion of catalyst withdrawn for treatment in said electrostatic separation step is a portion of at least partially regenerated catalyst.

` JOHN A. HATTON.

DONALD L. CLEVELAND. NORMAN'E. PEERY.

REFERENCES lCITED The' following references are of record in the le of this lpatent:

UNITED STATES PATENTS Williams Aug. 22, 1944 

